DD145051A5 - HERBICIDE MEDIUM - Google Patents

Abstract

A herbicidal mixture containing a herbicidal substituted anilide and substituted dichloroacetamide as antidote therefor, is disclosed.

Description

Berlin, 8.11.1979 55 921 12

A herbicidal agent application region D it Fiction dnung

The new herbicidal agents can be used in agriculture to control unwanted plant growth

Characteristic of the known technical solutions Substituted acetanilides of the formula I.

in the

R is hydrogen an unbranched or branched alkyl »? or alkoxy radical having up to 5 carbon atoms,

R is hydrogen, halogen, an unbranched or branched alkyl or alkoxy radical having up to 5 carbon atoms,

R is hydrogen,> halogen _{$ is} an unbranched or branched alkyl or alkoxy radical with up to 5 carbon atoms

R together with R has an ortho-connected ₉ given

, where appropriate, alkylene chain having up to 6 carbon atoms substituted by unbranched or branched alkyl groups of up to 4 carbon atoms,

.Vi raw -; α 7 α ^ W ^(: } /

2 1 # §41P * Berlin, the 0.11 »1979

55 921 12

A is an azole bonded via a ring nitrogen and which is monosubstituted or polysubstituted by halogen, phenyl, alkyl, alkoxy, alkylthio or perfluoroalkyl radicals each having up to 4 carbon atoms, cyano, carboxy, carbalkoxy having up to 4 carbon atoms in the alkoxy group or alkanoyl radicals with up to 4 carbon atoms, where A can also be salts of the 2 or 3 nitrogen atoms-containing azoles,

are herbicidally excellent but cause damage to the crops when applied to crops such as maize or to graminaceous crops.

Herbicidal agents which contain, in addition to chloroacetanilides as herbicidal active ingredient, antagonistic dichloroacetamides are known from DE-OS 22 18 097, DE-OS 24 02 983 and US Pat. No. 4 053 297 *

In DE-OS 22 18 097 v / ground, for example, combinations of antagonistic acting Η, Ν-diallyl-dichloroacetamide and some herbicidal acetanilides, such as 2 ~ chloro-2 ^f , 6 ^l ~ diäth3 '"l-l'j- (methoxy However, this dichloroacetamide and structurally similar dichloroacetamides are used as antidotes in combination with herbicidal thiolcarbamates

The subject of DE-OS 24 02 983 and US Pat. No. 4,053,297 are herbicidal compositions which already contain DE-OS 22 18 097 or which contain structurally similar dichloroacetamides together with chloroacetanilides of a different constitution. These compositions are suitable for selective weed control in corn,

Berlin, 8.11.1979 55 921 12

Aim of the invention

The aim of the invention was therefore to find antagonistic agents that compensate for this incompatibility of herbicidal acetanilides against certain crops.

Outline of the essence of the invention

The object of the invention is to provide novel herbicidal compositions with improved crop plant compatibility.

It has been found that dichloroacetamides of the formula II

in the R ¹ and R ²

R ¹ and

C-CHGl

II

are the same or different and may be a straight or branched alkyl radical having up to 6 carbon atoms which may be substituted by an alkoxy group having up to 4 carbon atoms or by a cyano group, an unbranched or branched alkenyl or alkynyl radical having up to 4 carbon atoms or a cycloalkyl radical with 3 to 6 carbon atoms or

together with the nitrogen atom of which they are substituents, a 4- to 9-membered, saturated mono- or bicylic ring which may be monosubstituted or polysubstituted by unbranched or branched alkyl radicals having up to 4 carbon atoms form »

SiM & MW -4- Berlin, '8.11.1979

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Herbicidal agents which contain at least one substituted acetanilide of the formula I and at least one dichloroacetamide of the formula II can be used both in maize and in cereal crops good herbicidal activity of the acetanilides obtained while damaging the crops are prevented.

Acetanilides whose crop plant tolerability can be improved by the dichloroacitamides of the formula II are those in which R is hydrogen, alkyl having up to * * carbon atoms, such as methyl, ethyl, n-propyl, i-propyl, n-butyl, sec. Butyl, i-butyl, tert-butyl, normal and branched pentyl, alkoxy of up to 5 carbon atoms such as methoxy, ethoxy, propoxy, butoxy, pentyloxy;

1 2

R and R are hydrogen, halogen, such as fluorine, chlorine, bromine or iodine, alkyl up to 5 carbon atoms, such as methyl, ethyl, n-propyl, i-propyl, n-butyl, sec-butyl, i-butyl, tert "-Butyl, n-pentyl and branched pentyl radicals, alkoxy having up to 5 carbon atoms such as methoxy, ethoxy, propoxy, butoxy j. pentyloxy; , ,

R together R is an ortho-linked, optionally substituted by alkyl having up to 4 carbon atoms alkylene chain having up to 6 carbon atoms, such as ethylene * trimethylene tetramethylene, 1-methyl-trimethylene, 1,1-dimethyl-trimethylene, 1,1-dimethyl tetramethylenj

X is chlorine or bromine, preferably chlorine and

£ - £ ν & 4P _ Berlin, 8.11.1979

55 921 12

A is an azole bonded via a ring nitrogen atom, such as pyrrole, pyrazole, imidazole, 1,2,4-triazole, 1,2,3-triazole, tetrazole, which is monosubstituted or polysubstituted by halogen, phenyl, alkyl, alkoxy , Alkylthio or perfluoroalkyl radicals each having up to 4 carbon atoms, cyano, carboxy, Carbalkozyreste having up to 4 carbon atoms in the alkoxy group or alkanoyl having up to 4 carbon atoms may be independently substituted, such as 2,6-dimethyl pyrrol, tetramethylpyrrole, 3 (5) -Methylpyrazole, 4-methylpyrazole, 3 (5) -ethylpyrazole, 4-ethylpyrazole, 3 (5) -isopropylpyrazole, 4-isopropylpyrazole, 3,3-dimethylpyrazole, 3,5-dimethyl-4- acetylpyrazole, 3,5-dimethyl-4-propionylpyrazole, 3 ', 4,5-trimethylpyrazole, 3 (5) -phenylpyrazole, 4-phenylpyrazole, 3'5'-diphenylpyrazole, 3 (5) -phenyl-5 (3) -methylpyrazole , 3 (5) TChlorpyrazole, 4-chloropyrazole, 4-bromopyrazole, 4-iodopyrazole, 3,4,5-trichloropyrazole, 3? 4? 5-tribromopyrazole, 3 ', 5-dimethyl-4-chloropyrazole, 3,5-dimethyl-4-bromopyrazole, 4-chloro-3 (5) -niethylpyrazole, 4-bromo-3 (5) -methylpyrazole, 4% methyl 3j5-dichloropyrazole, 3 (5) -methyl-4,5 (3) -dichloropyrazole, 3 (5) -chloro-5 (3) -methylpyrazole, 4-methoxypyrazole, 3 (5) -metliyl-5 (3) - metho3-pyrazole, 3 (5) -ethoxy-4,5 (3) -dimethylpyrazole, 3 (5) -methyl-5 (3) -trifluoromethyl-pyrazole, 3,5-bis-trifluoromethyl-pyrazol-3 (5) -methyl-5 (3) -carbethoxypyrazole, 3i5-Biscarbethoxypyrazole, 3 _s 4.5 ~ triscarbethoxypyrazole _i 3 (5) -methyl-5 (3) -methylthio-4-carbethoxypyrazole, 4-methyl-3i-5-biscarbethoxypyrazole, 4-cyanopyrazole, 4 ~ Metho3cy-3S5-dichlorpyrazol, 4y> 5-dichloro-imidazole _f 2-ethyl-4,5-dichloroimidazole, 2-methyl "4 _s 5-dichloroimidazole, 3 (5) -methyl ~ 1,2,4 triazole, 3 _? 5-dimethyl-1,2,4-triazole-1Si-chloro-1-triazole-3 (5) -bromo-1 _? 2 _? 4-triazole _s 3 (5) -chloro-5 (3) -methylol, 2,, 4-triazole, 3 * 5-dichloro-1 _? 2,4-triazoles 3,5-dibromo-1 (3) triazole (3i5) -chloro-5 (3) -cyano-1,2,4-triazole, 3 (5) -chloro-5 (3) -phenyl- 1 _s 2,4-triazole _g . 3 (5) -glomo-5 (3) -carbomethoxy »1,2,4-triazole, 3 (5) -methylthio-1 _f 2 _f 4-triazole-4 (5) -mothyl-1 _s 2,3 -t

4 14 * 49.-6- Berlin, 8.11.1979

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4.5 ~ dimethyl-1,2,3-triazole, 4 (5) -phenyl-1,2,3-triazole, 4 (5) -chloro-1,2,3-triazole, 1,2,3 ~ Triazole-4 (5) -yl-carboxylic acid ethyl ester, 1,2,3-triazole-4, 5-yl-dicarboxylic acid, methyl ester, 5-methyltetrazole, 5-chlorotetrazole, 'tetrazolyl-5-carboxylic acid ethyl ester,

In addition, when the optionally substituted azole contains 2 or 3 nitrogen atoms, the radical A may also be salted to one of the usual strong inorganic or organic acids such as hydrochloric acid, hydrobromic acid, nitric acid, sulfuric acid, tetrafluoroboric acid, fluorosulphonic acid, formic acid, a halogenated carboxylic acid , for "B _e trichloroacetic acid, an alkanesulfonic acid such. B »methanesulfonic acid, a halogenated alkanesulfonic acid, eg. B "trifluoromethanesulfonic acid perfluorohexanesulfonic acid, an arylsulfonic acid, e.g. B. dodecylbenzenesulfonic acid, be bound _e

Preference is given to acetanilides which carry methyl or ethyl in the 2- and 6-position on the phenyl ring and hydrogen, methyl or ethyl in the 3-position, azoles being pyrazole, imidazole, triazole or tetrazole, each being represented by lower alkyl, alkoxy , Carbalkoxy, cyano or halogen may be substituted come into consideration.

In particular, the herbicidal compositions according to the invention contain the following acetanilides:

2-chloro-2 ', 6'-dimethyl-N-pyrazol-1-yl-methyl-acetanilide, 2-chloro-2'-methyl-6'-ethyl-N ~ (pyrazol-1-ylmethyl) - acetanilide, 2-chloro-2 ^f, 6'-dimethyl-l- (4-methylpyrazol-1-yl-methyl) ~ _s acetanilide 2-chloro-2-methyl-6 ^{f f} ethyl-H- (4-methoxypyrazole -1-yl-methyl) -acetanilide, 2-chloro-2 »-methyl-6'-ethyl-N- (3 (5) -methylpyrazol-1-yl) -acetanilide _f 2-chloro-2 ^f ₉ 6 ^f dimethyl ~ li- (3.5 "" dimethylpyrazol-1-yl ~ raethyl) acetanilide,

&% mwmw -7-

Beriin, 8,11,1979 55 921 12

2 ~ Chloro-2 ', 6 »-dimethyl-1T- (1 ₈ 2,4-triazol-1-yl-methyl) ~ acetanilide, 2 ~ Chloro-2', ^6f -dimethyl-N- (4-chloropyrazole 1-yl-methyl) -acetanilide, 2-chloro-2- ^t ^ 'ö' -trimethyl-U-ipyrazol-1-ylmethyl) -acetanilide, 2-chloro-2 '-methyl-6'-ethyl-N- ( 3> 5-dimethyl-pyrazol-1-yl-methyl-acetanilide 2-chloro-2 ', 6'-diethyl-1-O-dimethyl-py-tazol-1-yl-methyl-ac-2-chloro-2 ', 3', 6'-trimethyl-FO, 5-dimethyl-pyrazol-T-yl-methyD-acetanilide, 2-chloro-2 ^r _s ^6! -diäthyl-U- (4-methylpyrazole-1-yl-methyD-acetanilide, 2-chloro-2-methyl-6 · ^f ethyl-N- (4-methylpyrazol-1-yl-methyl) -acetanilide ·, 2 Chloro-2 ', 3', 6 '-trimethyl-H- (4-kiethylpyrazol-1-yl-methyl) -acetanilide, 2-chloro-2', 6'-dimethyl-H- (3- (5) -methylpyrazol-1-yl-methyl) -acetanilide, 2-chloro-2 ^f _s, 6 ^t -diäthyl-N- (3- (5) -methylpyrazol-1-yl-methyl) -acetanilide, 2-chloro-2 ', o'-dimethyl-N - ^ -methoxypyrazol-1-ylmethyl) -aceta3iilide _s 2-chloro-2', ^6f -diethyl-H- (pyrazol-1-ylmethyl) -acetanilide, 2- chloro-2 _'f ^f 6-dimethyl-H- (4 (5-dich.lorimidazol-1-yl-methyl) -acetanilide, 2-chloro-2'-methyl-6-ethyl ^f Hi A "5-dichloroimidazole ~ 1-yl-methyl) -acetanilide, 2-chloro-2 »-methyl-6» -ethyl-N- (2-ethyl-4,5-dichloro-imidazol-1-ylmethyl) -acetanilide, 2-chloro 2 ^f, 6 ^l -diäthyl-H- (4f5-dichloroimidazole-i-yl ^ methyli-acetanilide, 2-chloro-2 ^f-6 methyl ethyl ^f-IT (1,2,4-triazo 1-1 yl methyl) acetanilide "2-chloro ~ 2 ^{f, f} 6 -diäthyl-H- (1, .2,4-triazol-1-yl-methyl) -acetanilide and 2-chloro-2 * 3 ¹ , ö'-trimethyl-Nd, 2,4-triazol-1-yl-methyl) -acetanilide

The acetanilides of the formula I are the subject of DE-OS

26 48 008 and the German patent application DE-OS

27 44 396. They can be obtained by reacting 2-halo-U-halomethylacetanilides of the formula III with a 1H-Azöl of the formula H-A according to the following reaction equation:

RJ ~ _ / ^c

CO-CH ₂ -S £ 2 ^ χ: XiO-CH ₂ -X

X 14 · «V. 8. Berlin, 8.1

55 921 12

1 2

The substituents R, R, R and X have the abovementioned meaning _; and A is an azole bonded via a ring nitrogen atom, which is monosubstituted or polysubstituted by halogen, phenyl, alkyl, alkoxy, alkylthio or perfluoroalkyl radicals having in each case up to 4 carbon atoms, cyano, carboxy or carbalkoxy radicals having up to 4 Carbon atoms in the alkoxy group or alkanoyl radicals may be substituted with up to 4 carbon atoms.

As antagonistic agents dichloroacetamides of the

1 2

mel II into account, in which the substituents R and R are the same or different and are an unbranched or branched eli alkyl of up to β CARBON fat omen _s, for example, methyl, ethyl, n-propyl, i-propyl, n-butyl, * ' i-butyl, sec-butyl, tert -butyl, n-hexyl, 1,4-dimethyl-n-butyl, an unbranched or branched alkenyl or alkynyl radical having up to 4 carbon atoms, for example alkyl, propargyl, i-methyl-butyne 2-yl, or a cycloalkyl radical having 3 to 6 carbon atoms, for example cyclopropyl, cyclohexyl,

The alkyl radicals may optionally be substituted by an alkoxy group having up to 4 carbon atoms, for example by methoxy, etioxy or by a cyano group. "The alkoxy group is preferably in the position of bonding of the carbon radicals".

1 2

R and R may together with the nitrogen atom whose substituents they are, a 4 ~ to 9-membered saturated mono- or bicyclischeri Räjig form _e This Keterocyclus can optionally substituted by straight-chain or branched alkyl having up to 4 carbon atoms, mono- or polysubstituted "Examples for these rings, piperidinyl, alkylpiperidinyl, for example 3,5-diethylpiperidinyl-5-azetidinyl-alkylacetidinyl, are included.

if ~ $, .- Berlin, 8.11. 1979

55 921 12

For example, 2,2,4-trimethylazetidinyl _f hexahydroazepinyl, alkyl-hexahydroazipinyl, for example, 3 »5» 5/3 _s 3,5 ~ tri-methyl-hexahydro-azepinyl, 2,3-methyl-hexahydroazepinyl, aza-bicyclof3,2 _? 2,3-nonyl, alkyl-aza-bicyclo-octyl, for example trimethyl-aza-bicyclo [3 »2, fjoctyl, 2 _P 5-dimethyl-pyrrolidinyl, aza-bicyclo [3,2, o-heptyl _e

Preferred antagonist is IT-isopropyl-lT-propargyl-dichloroacetamide.

The dichloroacetamides of Pormel II can be prepared by reacting the amines tf.er formula ⁽

1 2

in which R and R have the abovementioned meanings, be obtained with dichloroacetyl chloride. The reaction is carried out in a manner known per se in the presence of a chlorine-binding agent in an inert solvent or diluent.

Hydrogen chloride-binding agent, inorganic bases such as alkali metal carbonates _{s f} alkali metal hydrogen carbonates, alkali hydroxides, or organic bases, for example tertiary amines, such Trialkylaminej particular Triäthylamirii be ·

Suitable inert solvents or diluents are hydrocarbons, such as toluene, cyclohesan, halogenated hydrocarbons, such as methylene chloride, ethylene chloride and ethers, such as dioxane, tetrahydrofuran.

The following examples illustrate the preparation of dichloroacetamides

- ία -

Berlin, 8.11.1979 55 921 12

Ausführun gsbe ispiele Example 1

118 g of isopropyl-propargylamine and 123 g of triethylamine are dissolved in 670 ml of toluene. 180 g of dichloroacetyl chloride, dissolved in 450 ml of toluene, are added dropwise to this solution while cooling at room temperature. The mixture is allowed to react for one hour, filtered off with suction and washed the filtrate washed with water * the residue remaining after evaporation of the solvent residue is washed with petroleum ether, "is obtained 214 g of N-isopropyl-N-propargyl-dichloracetaniid, corresponding to a yield of 84% of th _e *; Kp _e 80-82 ° C / 0.013 mbar; S ehm .: 58 - 59 ⁰ G ₆

Example 2

20 g of hexamethyleneimine are dissolved in 150 ml of toluene and washed with 20 _? 2 g of triethylamine · Then v / ground at 0 ⁰ C 30 g of dichloroacetyl chloride was added dropwise _e mixture is stirred for 8 hours at 20 ⁰ C after filtered off, extracts the Piltrat with dilute hydrochloric acid, neutralized with sodium hydrogen carbonate solution and dried over sodium sulfate * After Concentrating under reduced pressure, one keeps an oil that crystallizes when rubbed in η-hexane "Schmp"? 57 ~ 58 ⁰ C; Yield 35 g, corresponding to 83 % of th, 1-dichloroacetylhexamethyleneimine ·

The following dichloroacetamides can be obtained in a corresponding manner:

Ii-C-CHCl

Il

R ¹ Berlin R ² , the 8. 11.1 979 CH ₂ = CH-CH ₂ - 55 921 CH ₂ = CH-CH ₂ - 12 Mr· HC ^ C-CH ₂ - HC ₃ H ₇ ) / Fp / n _D 1 HCs C-CH ₂ - (CHO) ₉ OH-CH ₉ -CH (CHO) - 1 ₉ 4990 2 HGe = C-CH ₂ - CH ₃ H ²⁶ y 1.4978 3 ! -C ₃ H ₇ C ₂ H ₅ n ²⁵ : 1.4889 4 ! -C ₃ H ₇ ! -C ₃ H ₇ n ²⁵ · ⁿ D * 1.5090 5 21 ^ C ₄ H ₉ O ₂ H ₅ n ²⁵ : 1.4849 6 SeC ^ -C ₄ H ₉ CH ₃ Fp: 62 - 65 ⁰ C 7 1-C ₄ H ₉ CH ₃ n ²⁵ : 1.4802 8th sec _e -C ₄ H ₉ HC-E = C-CH (CH ₃ ) - n ²⁵ : 1.4820 9 Ji-C ₄ H ₉ CHO n ²⁵ : 1.4820 10 HC = SC-CH ₂ - ⁿ D * 1.4923 11 - (CI: Ig) ₃ - _n 25. 1.4835 12 - (C Ig) ₄ - ". _n 25. 1.4960 13 ~ (C £ ^I 2 ⁾ 5 " Fp ι 37 - 39 ⁰ C 14 CH, , -CH- (CH 2) ₉ -CH-CH ₀ - H ²⁵ y 1.5190 15 Fp: 41 - 42 ⁰ C Fp: 101 -.102 ⁰ C

CH ₂ -CH ₂

-CH (CH ₃ J-CH ₂ -C (CH ₃ J ₂ - CH ₂ ClK CH ₃ J-CH ₂ -C (CH ₃ ) g -CHO-CH-

0

-CH (CH ₃ J- (CH ₂ J ₂ -CH (CH ₃ ) -CH _p -CH (C ₉ H ₁ -) -CHp-CH (C _p H _q )

Mp: 48 - 49 C mp 82-84 ⁰ C

Mp: 61-65 ⁰ C n | ⁵ i 1,5003

Berlin, 8,11,1979 55 921 12

No,

2

Kp / Fp / n _D

20 H ₃ CO-CH ₂ -CH ₂ H ₃ CO-CHg-CH ₂ - kp Vo, 4 «106 - 119 mbar 21 H ₃ CO-CHg-CH (CH ₃ ) - CH ₃ kp Vo, 53 - 103 - 112 ° mbar 22 H-CO-CSU-CH (CH,) - 5 £ j 1-C ₃ H ₇ Kp. ° C / O, 67 ϊ 1 _? 5028 0,013 mbar 23  .t> ' ~ Chg-teCH PP! - 75 ⁰ C • 117 24 tert "-C Hq "Chg ~ C"! H _n 25 s 1,4950 110 25 -t Π TT J. "" V / γ ^ -rr ^; o - i- : 1.4936 26 ^C 6 ^H 11 0- PP, ι 104 27 C ₆ H ₁ .j -Chg-CN PP! ! 98 28 -Chg-CN 29 -Chg-CN Pp ι 30 CgH ₅ -OH (CH ₃ ) CH-CH ₂ Kp! C / tert «-C ₄ H ₉ I -CH ₂ mbar -CH ₂ -CH t 132 ί 105 CH ₂ : 104 ί 73 -

~ ¹³ ~ Berlin, 8.11 _e 197S

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Tue, e antagonistic dichloroacetamides of formula II themselves have little or no visible effect on germination and growth of-both as a crop and unwanted plants, which are themselves at rates ₈ considerably above those polygamy are required to obtain an antagonistic effect * It but the ability to significantly reduce or completely eliminate the phytotoxicity of the herbicidal acetanilides of the formula to crops such as maize »

For herbicidal acetanilide which are less aggressive to the crop, lower level additions of anta "gonistischj active compounds or additives such compounds with lower antagonistic activity" That 'share ratio acetanilides ι dichloroacetamides can vary greatly "It depends both on the acetanilide and as well from the antagonist from ₀ Suitable proportions herbicidal active ingredient ϊ antagonistic compound are between 1: 2 to 1: 0.05 parts by weight _a

Acetanilides and dichloroacetamides can be incorporated into the soil together or separately, before or after sowing. "For the acetanilides of formula I, the most common method of application is application to the soil surface immediately after the seeds have been deposited or in the period between sowing and emergence young plants »Also a treatment during the casserole and shortly thereafter is possible. In any case, the compound having an antagonistic effect can be applied with the herbicidal active ingredient at the same time * Separate application in which the antagonist are placed on the field first, and then returns the herbicide or vice "· is possible _s such omission would not have much time that the herbicide has already caused damage to the crops *

- & ι m mmw - 14 -

, Berlin, 8.11.1979 55 921 12

Herbicide and antagonist may be present as sprays in suspendable, emulsifiable or soluble form or as granules, separately or jointly formulated. It is also conceivable treatment of crop seeds with the antagonist before sowing. The herbicide is then applied alone in the usual way.

The new herbicides can be used in addition to acetanilides}! and dichloroacetamides contain other herbicidal or growth-regulating active ingredients of a different chemical structure, for example 2-chloro-4-ethylamino-6-isopropyl-amino-1,3 $ 5-triazine, without the antagonistic effect of the dichloroacetamides being affected.

The compositions according to the invention or, when applied separately, the herbicidal active compounds or the antidote are used, for example, in directly sprayable solutions, powders, suspensions, even high-percentage aqueous, oily or other suspensions, or dispersions, emulsions, oil dispersions, pastes, dusts, scattering agents or Granules applied by spraying, atomizing, dusting, dispersing or pouring The application forms are based entirely on the intended use5 they should ensure the finest possible distribution of the agents according to the invention or "the individual components" in each Pail.

For the preparation of directly sprayable solutions, emulsions, pastes and oil dispersions come mineral oil fractions., From medium to high boiling point, such as kerosene, or diesel oil, coal tar oils and oils of vegetable or animal origin j aliphatic, cyclic and aromatic hydrocarbons, for example benzene, toluene, SyIo1, paraffin, tetrahydronaphthalene, alkylated naphthalenes or their derivatives, for example methanol, ethanol, propanol, butanol, chloroform, carbon tetrachloride, cyclohexanol, cyclohexanone, chlorobenzene, isophorone, strongly polar solvents *

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medium, vr. B ₄ dimethylformamide, dime thy lsulfoxid, IT-Me thy lpyrr olid _s on water, in Consider

Aqueous application forms can be prepared from emulsion concentrates, pastes or wettable powders (spray powders), old dispersions by addition of water. To prepare emulsions, pastes or oil dispersions, herbicidal active ingredient and / or antidote can be dissolved as such or in an oil or solvent. homogenized by Agitation, adhesives, dispersants or emulsifiers in water v / ground © but it is also from herbicidal active ingredient and / or antidote, Hetz ~ _s custody ", dispersant or emulsifier and, if made, solvent or oil, and such concentrates v / earths that are suitable for dilution with water ·

As surface-active substances come into consideration:

Alkali, alkaline _earth} ammonium salts of lignosulfonic _f naphthalenesulfonic _p phenolsulfonic acid, alkylarylsulfonates, alkyl sulfates, alkyl sulfonates, alkali metal and alkaline earth metal salts of dibutylnaphthalenesulfonic acid, Lauryläthersulfate, Fettalko "· alcohol sulfates, fatty acid alkali and alkaline earth metal salts, salts of sulfated hexadecanols. Heptadecanols, and octadecanols _s salts of sulfated fatty alcohol glycol ethers, Kondendationsprodukte of sulfonated naphthalene and Haphthalinderivaten with formaldehyde _t condensates of naphthalene, or "of the naphthalenesulfonic acids with phenol and formaldehyde, Polyoxyäthylenoctylphenoläther, ethoxylated isooctylphenol-octylphenol, Nony! Phenol, Alkj / lphenolpolyglykolätherj Tributylphenylpolyglykoläther, Alkalarylpolyätheralkohole, isotridecyl alcohol , Pettalkoholäthylenoxid condensates _s ethoxylated castor oil Polyoxyäthylenalkylather, ethoxylated Polyoxypropylenj lauryl alcohol Polyglykolätheracetal, sorbitol esters. Lignin, sulphite liquors and methylcellulose «

• Berlin, the 8.11 · 1979

55 921 12

Powders, dispersants and dusts may be prepared by mixing or co-grinding herbicidal active ingredient and / or antidote with a solid carrier.

Granules, s. B. Mmillillungs-, impregnating ™ and homogeneous granules can be prepared by binding the active compounds to solid carriers. "Solid carriers are eg." Mineral earths such as silica gel, silicic acids, silica gels, silicates, talc, kaolin, Attaclay, limestone, chalk, talc, Bolus, loess, clay, dolomite, diatomaceous earth _$ calcium and magnesium sulphate, magnesium oxide, ground plastics, fertilizer, such as e.g. Ammonium sulfate e _s ammonium nitrate _s ureas and vegetable products such as Getreidemehlej tree bark, wood and nutshell meal, cellulose powders and other solid carriers ·

The formulations contain between 0 _s and 95% by weight of herbicidal active ingredient and antidote, preferably between 0.5 and 90% by weight. The amounts of herbicidal herbicide are from 0.2 to 5 kg / ha _0. This amount of herbicidal active ingredient is taken together or separately , applied with such an amount of antidote, that the proportion of herbicidal active ingredient: antagonist compound is 1: 2 to 1: 0.05 parts by weight.

Examples of formulations are? ".

I. 3 parts by weight of the mixture of 8 parts by weight of 2-chloro-2 ', 6 ^l -dimethyl-N ~ (pyrazol-1-yl-methyl) -acet ~ anilide and one part by weight!, H-Diallyl-aichloracetamid be 97 Intimately mixed with parts by weight of finely divided kaolin. "This gives a dust containing 3% by weight of the active substance."

U ₀ 30 parts by weight of the mixture of one part by weight

^m * - 17 - Berlin, 8 * 11.1979

55 921 12

2-Chloro-2- ^F- methyl-6'-ethyl-N- (1,2,4-triazole-1-ynylethyl) -acetanilide and one part by weight of U-propargyl-H-isopropyl-dichloroacetamide are mixed with a mixture of 92 parts by weight of powdered silica. ßäureregel and 8 parts by weight of paraffin oil, which was sprayed onto the surface of this silica gel, intimately mixed * This gives a preparation of the active ingredient with good adhesion.

20 parts by weight of the mixture of one part by weight of 2-chloro-2'-methyl-6-ethyl-N- (4-chloro-5-dichloroimidazol-1-yl-methyl) -acetanilide and two parts by weight K _S H -Diallyl-dichloro-acetamide v / erden dissolved in a mixture of 80 parts by weight of XyIoI ₉ 10 parts by weight of the adduct of 8 to 10 moles of ethylene oxide to 1 mole of oleic H-momoäthanolamid, 5 parts by weight of calcium dodecylbenzenesulfonic acid and 5 parts by weight of the adduct of By pouring and finely distributing the solution in 100,000 parts by weight of water, an aqueous dispersion is obtained which contains 0.02% by weight of the active ingredient. ··

20 parts by weight of the mixture of four parts by weight of 2-chloro-2 ', β'-dimethyl-4-methoxypyrazol-1-yl-methyl-vacetanilide and one part by weight of U-propargyl-H-n-propyl-dichloroacetamide are dissolved in a mixture consisting of 40 parts by weight of cyclohexanone, 30 parts by weight of isobutanol, 20 parts by weight of the adduct of 7 moles of ethylene oxide with 1 mole of isooctylphenol and 10 parts by weight of the adduct of 40 moles of ethylene oxide with 1 mole of castor oil, Drexh pouring and finely divided The solution in 100,000 parts / parts by weight of water gives an aqueous solution

ί # 4β -18- Berlin, 8th Π .1979

55 921 12

Dispersion containing 0.02% by weight of the active ingredient ·

Greenhouse and field experiments show that the herbicidal compositions according to the invention increase the compatibility of the herbicidal acetanilides for the crop plants without reducing their herbicidal activity. "

I greenhouse experiments

Plastikpikierkisten of 51 cm Iänße _f 32 cm width and β cm height were β with loamy sand of pH and filled approximately 1.5% of humus "In this Substrs / fc corn was (CES mays) as a crop in rows sown shallow" Besides, barnyardgrass and non-sterilized soil additionally contained viable weed seeds that contributed to the population of unwanted plants. * This simulated a field crop planted with weeds and contaminated with weeds. «

The active compounds and the antagonistic compounds were applied both individually and in the mixtures described. They were emulsified or suspended in water as a carrier medium, sprayed onto the earth surface by means of finely distributing nozzles immediately after sowing and before the test plants were applied. In some cases, the agents were also mixed into the soil before sowing the crops. After sowing and treatment, the boxes were irrigated and covered with transparent plastic hoods until after planting. »This measure ensured uniform germination and growth of the plants«. Installation is carried out over a temperature range of 18 to 30 ° C on average.

" ¹⁹ " Berlin, 8.11.1979 55 921 12

The greenhouse experiments so observed were observed until the maize had developed 3 to 5 leaves. After this stage no further damage was to be expected with the herbicides, which was also confirmed in the field trials.

The mean exposure was rated on a scale of 0 to 100. Here 0 means normal and normal. Development of the plants, based on the untreated control "100 corresponds to a total absence of germination or" dying of the plants It had to be taken into account that Mais _β Β "occur in maize even under completely normal conditions and without any chemical treatment occasionally crippled or inhibited plants ,

The field trials were carried out on small plots on sites with loamy sand and loam of pH 5 to 6 and 1 to 1 5 % humus content. The pre-emergence treatments were carried out immediately at the latest 3 days after the crops were planted. ₀ The weed flora of various species composition was natural. However, only the dominant representatives were included in the tables. "Herbicides and antagonists and their combinations were emulsified or suspended in water as a carrier and distribution medium and applied by means of a motor-driven, tractor-mounted parcel sprayer irrigated to ensure a normal emergence of crops and weeds. "All trials ran over several months, so. that the development of the crop could be observed until seed formation "The evaluation of the agent effect was also made on the scale from 0 to 100"

Berlin, 8.11 * 1979

55 921 12

Result

The experimental results listed in detail in the following tables show that the antagonistic dichloroacetamides of the formula II, when used in combination with the herbicidal chloroacetanilides of the formula I, compensate for the incompatibility of these herbicides with the crop plants.

Due to the shallow cuttings of the crops and the more favorable conditions for the herbicidal activity conditions, the damage caused by the herbicides in the greenhouse were much more evident than in the field The testing of the antagonistic compounds was therefore harder in the greenhouse than in the field.

Table 1 - List of plant names

Botanical seed

Alopecurus myosuroides Chenopodium album Echinochloa crus galli Zea mays

German name

Field fox s chwan ζ White goosefoot Chicken millet

Corn

Final name

slender foxtail lambs quart ers bamyardgrass india corn

Table 2 - List of herbicidal acetanilides listed in the biological examples

CH ₂ -A C -CH ₉ Cl

IJ ^

designation

R ¹

II III

IY

CH

CH,

CH,

C ₂ H ₅

CH.

C ₂ H ₅

CH _c

CH-

CH,

CH-

CH-

H.H.

H H

TO!

from W

VJi φ

VD H

! S B "

ro

(D

VD

νο

Berlin, 8.11.1979 55 921 12

CJ

B "

H P

ο • Η

0)

H H

Table 3 - List of dichloroacetamides listed in the biological examples

designation

-CHp-CH = CH

_HC-0 O CHCl

ip¹VJAA-\ JXJ.r) "~\ JXi.n

-CH ₂ CH = CH

ro

\ y \ bd

fO H ·

co

VD

VD

Table 4 -.Verbesserung Corn compatibility τοπ 2 ~ chloro-2 ^f 6 ^f ~ dimethyl-H- (p; yrazol-1-yl-methyl) -acetanilide by an antagonistic effect dichloroacetamides in pre-emergence application in greenhouse

Test plants and % injury Crop undesirable plants Zea mays Echinochloa crusgalli

herbicidal Antagonistic application rate s Ί active substance acting Ver [Kg / ha bonds I 1.0. 2.0 I A 2 _f 0 0,125 + A 1,0 + 0.25 1,0 + 0.5 2,0 + I B 2.0 0.25 + B 1,0 + 1.0 1,0 + 0.5 2,0 +

63 78

34 22

0 41 25 50

100 100

100

100

100

ui ω

UI ©

VD H ro

lin

ro ρ,

(0

vo

Continuation of Table 4

Herbicidal Antagonist Drug Acting Compounds

Application rate [kg / ha a

Test plants and % Crop Cultivation of unwanted plants Zea mays Echinochloa crus galli

+. σ

2.0

1.0 + 0.125 1.0 + 0.25 1 ₉ 0 + 0.5 1.0 + 1.0 2.0 + 0.5

17 .13

7 12 23

O 55 921 ! Berlin, 98 ro ro the 97 i 96 100. 100

Table 5 - Improvement of the crop plant compatibility of herbicidal acetanilides in the case of green-field application in the greenhouse by antagonistic, acting dichloroacetamides

Herbicidal agents

Antagonistic compounds

Application rate (kg / ha Tes'tpf lanzen and % damage crop unwanted plants

Zea mays Alopecurus Echinochloa crus myosuroides galli.

II

II

+ C

III

III

1, O 125 2, O 25 1, O H 0 1, O H 5 1, O H 2, O H oh, H 0, H 2, h 0,

1.0

1.0 H 1.0 H 1.0 H 2.0 H t-0.125 I · 0.25 ! - 1,0 i- 0.5

50 63

5 3

5 5

30 47

2 2 7

95

98 96 85 98

88 99

80

88

84

100

99 55 921 1 1 ro -3. I 98 98 ro 98 Berlin, 98 99. 99 p- 99 co • 99 • VO 99 VO 100

Continuation of Table 5,

Herbicidal Antagonist Application rate of active ingredients Contaminants / ha a compounds Test plants and % damage

e undesirable plants Zea mays Alopecurus Echinochloa crus myosuroides. galli

IV

IV

+ c

+ C

1.0 • I · 0.125 17 90 2 _s 0 r 1.0 42 90 1.0 H I · 0.5 2 89 1.0 H 5 88 2.0 H 6 92 1.0 : · 0.25 60 90 2.0 h 1.0 65 94 1,0 -: t-0.5 7 90 1.0 H 5 92 2.0 η 7 98

99 VJL VJI VO ro I ro co 99 ro 'ί VO VO VO VO Berlin,. 100 8.1 99 99 99 * 99 99 VO VD

Continuation of the table

Herbicides Antagonistically active compounds

Application rate kg / ha a. sj

Test plants and % damage crop plant unmerited plants

Zea mays Alopecurus Echinochloa crus myoauroideg galli

VI

VI YII

VII VIII

VIII

+ σ

1.0 73 98 2.0 · 85 98 1.0 H 18 93 1.0 35 94 2.0 55 98 1.0 H 2 84 1.0 12 85 2.0 25 90 1.0 H 5 80 2.0 H 2 se h 1.0 h 1.0 h 0.125 ^ 0,25

99 99

98 vn ro (D VJL 1 H H 99 VD 99 ro " _j. the ro CX) 99 98 KO 99 VO 98 98

Continuation of Table 5

Herbicidal antagonistically active compounds

Application rate] kg / ha a. Test plants and % damage crop unwanted plants

Zea mays Alopecurus Echinochloa crus myosuroides galli

IX

1 ₉ 0 125 80 2.0 0 82 1.0 π 5 5 1.0 H 2.5 2.0 η 5 l · 1, h 0,

90 95

98 98 99

99 100

98 98 98

0 S = no damage 100 s Plants did not accumulate or died

Table β - Improvement of Compatibility of 2 ~ Chloro-2 ^! , 6 * -dimethyl-li- (pyrazol-1-yl-methyl) - »acetanilide for maize by antagonistic 'acting' dichloroacetamides in pre-emergence application in the field

.Herbicidal active ingredient

Antagonistic compounds

Application rate of test plants and % damage jkg / ha. a * si} crop undesirable plants

Zea mays Echinochloa crus Chenopodium '. galli album

+ C

2.0 3.0 4.0 4.0 2.0 η 2.0 η 3.0 π 4,0 H 4.0 2.0 η 2.0 H 3.0 η 4.0 η I · 0.5 H 1.0 h 1.0 l · 1.0 h 0.5 H 1 * 0 H 1.0 r 1.0

37 39

0 19 10

25 42

 6

18

18

99 100 100.

100 100 100

mm

100 100 100 100

0 = normal rise and growth; 100 = plants did not accumulate or died

vji ro ro η ·

"A _i

ro &

Claims (1)

R is hydrogen, an unbranched or branched alkyl or alkoxy radical having up to 5 carbon atoms, R is hydrogen, halogen, an unbranched or branched alkyl or alkoxy radical having up to 5 carbon atoms, R is hydrogen, halogen, an unbranched or branched alkyl or alkoxy radical having up to 5 carbon atoms f R together with R denotes an ortho-linked alkenylene chain having up to 6 carbon atoms, optionally substituted by unbranched or branched alkyl groups having up to 4 carbon atoms, X is chlorine or bromine and A is an azole bonded via a ring nitrogen atom, which is monosubstituted or polysubstituted by halogen, phenyl, alkyl, alkoxy, alkylthio or perfluoroalkyl radicals each having up to 4 carbon atoms, cyano, carboxy, carbalkoxy having up to 4 carbon atoms in the alkoxy group or alkanoyl radicals to may also be substituted by salts of the 2 or 3 nitrogen atoms-containing azoles _s Jt Ι4έ4® ~ 33 - Berlin, the .8.11 »1979 55 921 12 as a herbicidal active ingredient and a dichloroacetamide of the formula II
.1 ^V 'HC-CHCl ₂ II, it <~ in the 1? R and R are the same or different and are an unbranched or branched alkyl radical having up to 6 carbon atoms which may be substituted by an alkoxy group having up to 4 carbon atoms or by a cyano group, an unbranched or branched alkenyl or mean or a cycloalkyl group having 3 to 6 carbon ^atoms: alkynyl of up to 4 carbon atoms 12 R and R together with the nitrogen atom of which they are substituents form a 4- to 9-membered, saturated mono- or bicyclic ring which may be monosubstituted or polysubstituted by unbranched or branched alkyl radicals having up to 4 carbon atoms, as an antagonistic agent, wherein the proportion by weight of acetanilide: dichloroacetamide is 1: 2 to 1 · j 0.05 parts by weight »